EP2935470A1 - Composition formant une couche isolante et son utilisation - Google Patents

Composition formant une couche isolante et son utilisation

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Publication number
EP2935470A1
EP2935470A1 EP13811834.4A EP13811834A EP2935470A1 EP 2935470 A1 EP2935470 A1 EP 2935470A1 EP 13811834 A EP13811834 A EP 13811834A EP 2935470 A1 EP2935470 A1 EP 2935470A1
Authority
EP
European Patent Office
Prior art keywords
component
tris
composition
composition according
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP13811834.4A
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German (de)
English (en)
Inventor
Sebastian Simon
Armin Pfeil
Thomas Bürgel
Angela Mücke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hilti AG
Original Assignee
Hilti AG
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Filing date
Publication date
Application filed by Hilti AG filed Critical Hilti AG
Publication of EP2935470A1 publication Critical patent/EP2935470A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints

Definitions

  • Compositions are usually applied to the formation of coatings on the surface of components to protect them from fire or against large heat exposure, for example as a result of a fire.
  • Steel structures are now an integral part of modern architecture, even if they have a major disadvantage compared to reinforced concrete construction. Above about 500 ° C, the load bearing capacity of the steel decreases by 50%, i.e., 50%. The steel loses its stability and carrying capacity. This temperature can be reached after about 5-10 minutes, depending on the fire load, such as direct fire (about 1000 ° C), which often leads to a loss of capacity of the construction.
  • the aim of fire protection, especially of steel fire protection is to delay the period of time until the loss of bearing capacity of a steel structure in case of fire to save human lives and valuable goods as long as possible.
  • F-classes such as F 30, F 60, F 90 (fire resistance classes according to DIN 4102-2) or American classes according to ASTM etc.
  • F 30 means that a load-bearing steel construction must withstand fire for at least 30 minutes in the event of a fire under standard conditions. This is usually achieved by delaying the heating rate of the steel, e.g. B. by coating the steel structure with intumescent coatings. These are paints whose components foam in the event of fire to form a solid microporous carbon foam.
  • Essential for the achievable fire resistance is always the applied layer thickness of the coating, or the resulting ash crust.
  • the coatings In order to meet the required fire resistance times, the coatings must have a certain thickness and the ability to form a voluminous and thus well insulating ash crust when exposed to heat, which remains mechanically stable over the period of fire stress.
  • binders usually resins
  • solvent-based or water-based systems binders, usually resins, are applied to the component as a solution, dispersion or emulsion. These can be implemented as single or multi-component systems. After application, the solvent or water evaporates leaving a film that dries over time.
  • the 100% systems contain the components of the binder without solvent or water. They are applied to the component, wherein the "drying" of the coating takes place only by reaction of the binder components with one another.
  • the solvent or water-based systems have the disadvantage that the drying times, also called hardening times, are long and, in addition, several layers have to be applied, that is, require several operations in order to achieve the required layer thickness. Since each layer must be dried accordingly before the application of the next layer, this leads to a high expenditure on working time and correspondingly high costs and a delay in the completion of the structure, as sometimes pass several days, depending on climatic conditions, until the required layer thickness is applied.
  • Another disadvantage is that due to the required layer thickness, the coating may tend to crack and flake during drying or exposure to heat, whereby in the worst case the substrate is partially exposed, especially in systems where the binder does not evaporate after evaporation of the solvent or of the water.
  • the invention is therefore an object of the invention to provide a coating system of the type mentioned, which avoids the disadvantages mentioned, in particular is not solvent or water-based and has a rapid curing, due to appropriately tuned viscosity is easy to apply and requires only a small layer thickness due to the high intumescence, ie the formation of an effective ashes crust layer.
  • the invention accordingly provides an intumescent composition
  • a constituent A containing at least one compound having one or more reactive carbon multiple bonds, such as a CC double bond or a CC triple bond, per molecule and optionally at least one reactive diluent, with a constituent B, the at least one thiol-functionalized compound having an average number of thiol groups per molecule of at least 2, and containing a radical initiator, and a component C containing an intumescent additive.
  • compositions according to the invention By means of the composition according to the invention, coatings having the required layer thickness for the respective fire resistance duration can be applied in a simple and fast manner.
  • the advantages achieved by the invention are essentially to be seen in the fact that the working time can be considerably reduced by packaging the composition as a two-component or multicomponent system and by the fast curing times inherent in multicomponent systems based on radically polymerisable resins. Due to the low viscosity of the composition in the application range, adjusted via suitable thickener systems, in contrast to epoxy-amine systems, application without heating the composition is possible, for example, by the widespread airless spray method. A further advantage is that it is possible to largely dispense with substances which are hazardous to health and have to be labeled, for example critical amine compounds.
  • compositions of the present invention show excellent adhesion to various metallic and non-metallic substrates as well as excellent cohesion and impact resistance.
  • a "reactive CC double bond or CC triple bond” is a CC double or triple bond which is not aromatic
  • chemical intumescence means the formation of a voluminous, insulating ash layer by means of coordinated compounds which react when exposed to heat
  • physical intumescence means the formation of a voluminous, insulating layer of ash by puffing up a compound that, without being a chemical
  • Carbon dioxide and water burns are also referred to as " carbon skeleton ", and " acid generator " is a compound which forms a nonvolatile acid under heat, ie above about 150 ° C, for example, by decomposition, thereby acting as a catalyst for carbonification; In addition, it can contribute to lowering the viscosity of the melt of the binder;
  • the term "dehydrogenation catalyst” is used hereby equivalently, -
  • a "blowing agent” is a compound which decomposes at elevated temperature with evolution of inert, ie non-combustible gases and optionally the softened binder inflates to a foam (intumescence); synonymous with “gas generator”used;
  • an "ash crust stabilizer” is a so-called scaffold-forming compound which stabilizes the carbon skeleton formed by the interaction of carbon formation from the carbon source and the gas from the propellant, or the physical intumescence The addition of such an ash crust stabilizer contributes to a
  • 'Radical initiator' means a radical source which undergoes radiation-induced thermal decomposition or thermal decomposition to form radicals by means of a catalyst (accelerator), - '(meth) acrylic ... / ... (meth) acrylic ...' Methacryl .. J ... methacryl ... "- as well as the” acrylic .. J ... acrylic ... "compounds should be included.
  • a compound having at least one C-C double bond or a C-C triple bond is used as a compound with reactive carbon multiple bonds, which can cure radically and is sufficiently stable on storage due to the lack of homopolymerization.
  • Suitable compounds are described in WO 2005/100436 A1 and WO 2007/042199 A1, the contents of which are hereby incorporated into this application.
  • the compound having reactive carbon multiple bonds is a compound having at least one non-aromatic C-C double bond, such as (meth) acrylate-functionalized compounds, allyl-functionalized compounds, vinyl-functionalized compounds, norbornene-functionalized compounds and unsaturated polyester compounds ,
  • Examples of unsaturated polyester compounds are the article by M. Maik et al. J. Macromol. Sei., Rev. Macromol. Chem. Phys. 2000, C40, 139-165, in which a classification of such compounds has been made on the basis of their structure, wherein five groups are named: (1) ortho resins, (2) iso resins, (3) bisphenol A fumarate, (4) chlorendics, and (5) vinyl ester resins. Of these, the so-called dicyclopentadiene (DCPD) resins can be further distinguished.
  • DCPD dicyclopentadiene
  • the compound having reactive carbon multiple bonds comprises allyl, vinyl, (meth) acrylic, fumaric, maleic, itaconic, crotonic or cinnamic double bond units, or the compound having reactive carbon multiple bonds is a Diels-Alder adduct or Norbornene derivative thereof or a derivative thereof with another compound bearing bicyclic double bonds.
  • exemplary compounds are vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinylamines, allylamines, vinylamides, esters and amides of (meth) acrylic acid, esters of fumaric acid and maleimides.
  • the unsaturated compound is particularly preferably selected from the group consisting of trimethylolpropane diallyl ether, pentaerythritol triallyl ether, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane diallyl ether, diallyl phthalate, succinyl diallyl ester, bis (4- (vinyloxy) butyl] adipate, bis [4- (vinyloxy) butyl] ester, isophthalic acid bis [4 (vinyloxy) butyl] ester, terephthalic acid bis [4- (vinyloxy) butyl] ester, trimellitic tris [4- (vinyloxy) butyl] ester, diethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol allyl
  • the composition contains other low viscosity compounds as reactive diluents to adjust the viscosity of the composition, if necessary.
  • a reactive diluent as a pure substance or in a mixture, low-viscosity compounds can be used, which react with the components of the composition. Examples are allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic esters and thiol-functionalized compounds.
  • Reactive diluents are preferably selected from the group consisting of allyl ethers such as allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl phenyl ether, allyl benzyl ether, trimethylol propane allyl ether, allyl ester such as allyl acetate, allyl allyl, maleate, allyl acetoacetate, vinyl ethers such as butyl vinyl ether, 1,4-butanediol vinyl ether, tert-butyl vinyl ether , 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether, diethylene glycol vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, propyl vinyl ether, ethyl 1-propenyl ether, dode
  • the compound having one or more reactive C-C double bonds or C-C triple bonds per molecule further contains a compound for preventing the early polymerization of the unsaturated compound, the so-called stabilizer.
  • Suitable stabilizers according to the invention are the inhibitors customarily used for free-radically polymerizable compounds, as are known to the person skilled in the art.
  • the stabilizers are selected from phenolic compounds and non-phenolic compounds, such as stable radicals and / or phenothiazines.
  • Phenolic inhibitors which are often constituents of commercial free-radically curing reaction resins, are phenols, such as 2-methoxyphenol, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol.
  • phenothiazines such as phenothiazine and / or derivatives or combinations thereof
  • stable organic radicals such as galvinoxyl and / V-oxyl radicals into consideration.
  • Suitable stable / V-oxyl radicals can be prepared from 1-oxyl-2,2,6,6-tetramethylpiperidine, 1 -Oxyl-2,2,6,6-tetramethylpiperidin-4-ol (also referred to as TEMPOL), 1 -Oxyl-2,2,6,6-tetramethylpiperidin-4-one (also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxy-piperidine (also 4-carboxy-TEMPO 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1 -Oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also referred to as 3-carboxy-PROXYL), aluminum / V- nitrosophenylhydroxylamine, diethylhydroxylamine.
  • TEMPOL 1 -Oxyl-2,2,6,6-tetramethylpiperidin-4-ol
  • TEMPON 1 -
  • suitable / V-oxyl compounds are oximes, such as acetaldoxime, acetone oxime, methyl ethyl ketoxime, salicyloxime, benzoxime, glyoximes, dimethylglyoxime, acetone-O- (benzyloxycarbonyl) oxime or pyrimidinol or pyridinol compounds substituted in the para-position to the hydroxyl group, as they are are described in the non-prepublished patent DE 10 201 1 077 248 B1, and the like.
  • the inhibitors may be used either alone or in combination of two or more thereof.
  • any compound which has at least two thiol groups can be used as the thiol-functionalized compound.
  • Each thiol group is attached either to a backbone, either directly or through a linker, and the thiol-functionalized compound of the present invention may have any of a wide variety of scaffolds, which may be the same or different.
  • the framework is a monomer, an oligomer or a polymer.
  • the frameworks comprise monomers, oligomers or polymers having a molecular weight (Mw) of 50,000 g / mole or less, preferably 25,000 g / mole or less, more preferably 10,000 g / mole or less, even more preferably 5,000 g / mol or less, even more preferably 2,000 g / mol or less, and most preferably 1,000 g / mol or less.
  • Mw molecular weight
  • monomers suitable as skeletons there may be exemplified alkanediols, alkylene glycols, sugars, polyvalent derivatives thereof or mixtures thereof, and amines such as ethylenediamine and hexamethylenediamine, and thiols.
  • oligomers or polymers suitable as skeletons there may be exemplified polyalkylene oxide, polyurethane, polyethylene vinyl acetate, polyvinyl alcohol, polydiene, hydrogenated polydiene, alkyd, alkyd polyester, (meth) acrylic polymer, polyolefin, polyester, halogenated polyolefin, halogenated polyester, polymercaptan , as well as copolymers or mixtures thereof.
  • the backbone is a polyhydric alcohol or a polyvalent amine, which may be monomeric, oligomeric or polymeric. More preferably, the backbone is a polyhydric alcohol.
  • alkanediols such as butanediol, pentanediol, hexanediol
  • alkylene glycols such as ethylene glycol, propylene glycol and polypropylene glycol
  • glycerol 2- (hydroxymethyl) propane-1,3-diol, 1, 1, 1 -Tris (hydroxymethyl) ethane, 1, 1, 1-trimethylolpropane, di (trimethylolpropane), tricyclodecanedimethylol, 2,2,4-trimethyl-1, 3-pentanediol, bisphenol A, cyclohexanedimethanol, alkoxylated and / or ethoxylated and / or propoxylated derivatives of neopentyl glycol, tetraethylene glycol cyclohexanedimethanol, hexanediol,
  • linkers any units which are suitable for linking skeleton and functional group can be used.
  • the linker is preferably selected from structures (I) to (XI). 1: binding to the functional group
  • the functional group is the thiol group (-SH).
  • Particularly preferred thiol-functionalized compounds are esters of ⁇ -thioacetic acid (2-mercaptoacetates), ⁇ -thiopropionic acid (3-mercaptopropionates) and 3-thiobutyric acid (3-mercaptobutyrates) with monoalcohols, diols, triols, tetraols, pentaols or other polyols and 2 -Hydroxy-3-mercaptopropyl derivatives of monoalcohols, diols, triols, tetraols, pentaols or other polyols.
  • Mixtures of alcohols can also be used as the basis for the thiol-functionalized compound.
  • WO 99/51663 A1 the contents of which are hereby incorporated by reference.
  • thiol-functionalized compounds may be mentioned by way of example: glycol bis (2-mercaptoacetate), glycol bis (3-mercaptopropionate), 1, 2-propylene glycol bis (2-mercaptoacetate), 1, 2-propylene glycol bis (3-mercaptopropionate), 1, 3
  • the thiol-functionalized compound can be used alone or as a mixture of two or more different thiol-functionalized compounds.
  • the reaction between the at least one radically polymerizable compound having one or more reactive carbon multiple bonds and the at least one thiol-functionalized compound is initiated by a radical initiator.
  • Suitable radical initiators are all compounds known to those skilled in the art, which are radiation-induced, form radicals by thermal or catalytic decomposition.
  • the radical initiator is a compound which forms radicals by thermal or catalytic decomposition. More preferably, the radical initiator is a compound which forms radicals by catalytic decomposition.
  • photoinitiators examples include benzoin and substituted derivatives thereof, benzophenones, 4,4'-bis (dimethylamino) benzophenone, dialkoxybenzophenones, dialkoxyacetophenones, peroxyesters as described, for example, in US 4,616,826 and US Pat 4,604,295 are described.
  • benzophenone acetophenone, acenapthenequinone, o-methoxybenzophenone, thioxanthen-9-one, xanthen-9-one, 7H-benz [de] anthracen-7-one, dibenzosuberone, 1-naphthaldehyde, 4,4 '- bis (dimethylamino) benzophenone, fluoren-9-one, 1'-acetonaphthone, 2'-acetonaphthone, anthraquinone, 1-indanone, 2-th / f-butylanthraquinone, valerophenone, hexanophenone, 8-phenylbutyrophenone, p-morpholinopropiophenone, 4-morpholinobenzophenone, 4'-morpholinodeoxybenzoin p-diacetylbenzene, 4'-methoxyacetophenone,
  • Thermal radical initiators include peroxides, azonitriles and similar free radical initiators known in the art, with peroxides being preferred.
  • the peroxides used to initiate the curing reaction can be any peroxide known to those skilled in the art for use in curing unsaturated compounds. Such peroxides include organic and inorganic peroxides, either solid or liquid. Hydrogen peroxide can also be used. Examples of suitable peroxides are peroxycarbonates (of the formula -OC (O) OO-), peroxyesters (of the formula -C (O) OO-), diacyl peroxides (of the formula -C (O) OOC (O) -), dialkyl peroxides (of the formula -00-) and the like. These may also be oligomeric or polymeric in nature. An extensive set of examples of suitable peroxides can be found, for example, in US 2002/0091214 A1, paragraph [0018].
  • the peroxide is preferably a hydroperoxide, a perether, a perester, a peranhydride or a percarbonate, more preferably the peroxide is selected from the group of percarbonates, peresters and hydroperoxides and most preferably the peroxide is a mono-percarbonate such as terf-butylperoxy 2-ethylhexyl carbonate, or a perester such as te / f-butyl peroxybenzoate.
  • the composition of the invention preferably further comprises a transition metal compound as an accelerator or curing catalyst. The presence of such a transition metal compound is advantageous in that it accelerates the decomposition of the peroxide and thus the curing of the resin composition.
  • the transition metal is preferably selected from the transition metals whose atomic numbers are from an atomic number in the range of 22 to 29 or one Atom number in the range of 38 to 49 or an atomic number in the range of 57 to 79 range. Most preferably, the transition metal is selected from V, Mn, Cu, Fe.
  • compositions may contain a co-accelerator, such as 1,3-dicarbonyl compounds, e.g. 1,3-diketones and aldehydes, especially acetylacetone, benzoylacetone and dibenzoylmethane; Mono- and diesters, especially diethyl malonate and succinates, acetoacetates, such as ethyl acetoacetate, acetoxyacetylethyl methacrylate and the like, to further increase the reactivity, if necessary.
  • constituent C contains an intumescent additive, which additive may comprise both individual compounds and a mixture of several compounds.
  • intumescent additives Suitably used as intumescent additives are those which are prevented or at least delayed by the formation of a heat-generating, inflated, insulating layer of flame-retardant material which protects the substrate from overheating and thereby altering the mechanical and static properties of structural components.
  • a heat-generating, inflated, insulating layer of flame-retardant material which protects the substrate from overheating and thereby altering the mechanical and static properties of structural components.
  • a voluminous, insulating layer namely an ash layer
  • the voluminous insulating layer can be formed by physical intumescence. Both systems can be used alone or together as a combination according to the invention.
  • an intumescent layer by chemical intumescence generally requires at least three components, a carbon source, a dehydrogenation catalyst, and a propellant, which are included in a binder, for example, in coatings.
  • a carbon source When exposed to heat, the binder softens and the fire protection additives are released so that they can react with each other in the case of chemical intumescence or inflate in the case of physical intumescence.
  • Thermal decomposition from the dehydrogenation catalyst forms the acid which serves as a catalyst for the carbonification of the carbon source.
  • the blowing agent decomposes thermally to form inert gases, the causing inflation of the carbonized (charred) material and optionally the softened binder to form a voluminous, insulating foam.
  • the intumescent additive comprises at least one carbon back forming agent, if the binder can not be used as such, at least one acid generator, at least one propellant, and at least one inorganic scaffold.
  • the components of the additive are selected so that they can develop synergism, with some of the compounds capable of performing several functions.
  • Suitable carbon sources are the compounds commonly used in intumescent fire-retardant formulations and known to those skilled in the art, such as starch-like compounds, e.g. Starch and modified starch, and / or polyhydric alcohols (polyols), such as saccharides and polysaccharides and / or a thermoplastic or thermosetting polymeric resin binder, such as a phenolic resin, a urea resin, a polyurethane, polyvinyl chloride, poly (meth) acrylate, polyvinyl acetate, polyvinyl alcohol, a silicone resin and / or a rubber.
  • starch-like compounds e.g. Starch and modified starch
  • polyhydric alcohols polyols
  • polyols such as saccharides and polysaccharides and / or a thermoplastic or thermosetting polymeric resin binder, such as a phenolic resin, a urea resin, a polyurethane, polyvinyl chloride, poly
  • Suitable polyols are polyols from the group consisting of sugar, pentaerythritol, dipentaerythritol, tripentaerythritol, polyvinyl acetate, polyvinyl alcohol, sorbitol, polyoxyethylene / polyoxypropylene (EO-PO) polyols. Preference is given to using pentaerythritol, dipentaerythritol or polyvinyl acetate.
  • binder itself may also have the function of a carbon supplier in case of fire.
  • Suitable dehydrogenation catalysts or acid formers are the compounds conventionally used in intumescent fire-retardant formulations and known to those skilled in the art, such as a salt or an ester of an inorganic, non-volatile acid selected from sulfuric acid, phosphoric acid or boric acid.
  • phosphorus-containing compounds are used whose range is very large, as they extend over several oxidation states of the phosphorus, such as phosphines, phosphine oxides, phosphonium compounds, phosphates, elemental red phosphorus, phosphites and phosphates.
  • phosphoric acid compounds may be mentioned by way of example: monoammonium phosphate, diammonium phosphate, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine resin phosphates, potassium phosphate, Polyol phosphates such as pentaerythritol phosphate, glycerol phosphate, sorbitol phosphate, mannitol phosphate, dulcitol phosphate, neopentyl glycol phosphate, ethylene glycol phosphate, dipentaerythritol phosphate and the like.
  • the phosphoric acid compound used is preferably a polyphosphate or an ammonium polyphosphate.
  • Melamine resin phosphates are compounds such as reaction products of Lamelite C (melamine-formaldehyde resin) with phosphoric acid.
  • sulfuric acid compounds there may be exemplified ammonium sulfate, ammonium sulfamate, nitroaniline bisulfate, 4-nitroaniline-2-sulfonic acid and 4,4-dinitrosulfanileamide, and the like.
  • boric acid compound melamine borate can be exemplified.
  • Suitable blowing agents are the compounds customarily used in fire protection formulations and known to the person skilled in the art, such as cyanuric acid or isocyanic acid and its derivatives, melamine and derivatives thereof.
  • cyanuric acid or isocyanic acid and its derivatives such as cyanuric acid or isocyanic acid and its derivatives, melamine and derivatives thereof.
  • Such are cyanamide, dicyanamide, dicyandiamide, guanidine and its salts, biguanide, melamine cyanurate, cyano acid salts, cyanic acid esters and amides, hexamethoxymethylmelamine, dimelamine pyrophosphate, melamine polyphosphate, melamine phosphate.
  • Hexamethoxymethylmelamine or melamine (cyanuric acid amide) is preferably used.
  • the intumescent additive comprises at least one thermally expandable compound, such as a graphite intercalation compound, also known as expandable graphite. These can also be incorporated into the carrier material.
  • expandable graphite for example, known insertion compounds of SO x , ⁇ , halogen and / or strong acids in graphite come into question. These are also referred to as graphite salts. Preference is given to expandable graphites which release S0 2 , S0 3 , NO and / or N0 2 at temperatures of, for example, 120 to 350 ° C. while being swelled.
  • the expandable graphite for example, in the form of platelets with a maximum Diameter in the range of 0, 1 to 5 mm are present. Preferably, this diameter is in the range 0.5 to 3 mm. Expandable graphites suitable for the present invention are commercially available.
  • the expandable graphite particles are evenly distributed in the fire protection elements according to the invention.
  • concentration of expandable graphite particles can also be varied selectively, pattern-like, areally and / or sandwich-like.
  • EP 1489136 A1 the contents of which are hereby incorporated by reference.
  • the insulating layer is formed by both chemical and physical intumescence, such that the intumescent additive comprises both a carbon source, a dehydrogenation catalyst and a blowing agent, as well as thermally expandable compounds.
  • the intumescent additive comprises both a carbon source, a dehydrogenation catalyst and a blowing agent, as well as thermally expandable compounds.
  • an oxide or a compound of a metal from the group comprising aluminum, magnesium, iron or zinc may be used, in particular iron oxide, preferably iron trioxide, titanium dioxide, a borate, such as zinc borate and / or a glass frit of low-melting glasses a melting temperature of preferably at or above 400 ° C, phosphate or sulfate glasses, Melaminpolyzinksulfaten, Ferrogläsern or Calziumborosilikaten.
  • the addition of such an ash crust stabilizer contributes to a substantial stabilization of the Ash crust in case of fire, since these additives increase the mechanical strength of the intumescent layer and / or prevent their dripping. Examples of such additives can also be found in US Pat. Nos. 4,442,157 A, 3 562 197 A, GB 755 551 A and EP 138 546 A1.
  • ash crust stabilizers such as melamine phosphate or melamine borate, may be included.
  • one or more reactive flame retardants may be added to the composition of the invention.
  • Such compounds are incorporated in the binder.
  • An example within the meaning of the invention are reactive organophosphorus compounds, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives, such as DOPO-HQ, DOPO-NQ, and adducts.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • DOPO-HQ 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • DOPO-HQ 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • DOPO-HQ DOPO-HQ
  • DOPO-NQ DOPO-NQ
  • the intaglio-forming additive may be contained in an amount of from 30 to 99% by weight in the composition, the amount depending substantially on the application form of the composition (spraying, brushing and the like).
  • the proportion of ingredient C in the overall formulation is set as high as possible.
  • the proportion of constituent C in the overall formulation is preferably from 35 to 85% by weight and more preferably from 40 to 85% by weight.
  • the composition may optionally contain conventional auxiliaries, such as solvents, such as xylene or toluene, wetting agents, for example based on polyacrylates and / or polyphosphates, antifoams, such as silicone defoamers, thickeners, such as alginate thickeners, dyes, fungicides, plasticizers, such as chlorine-containing waxes , Binders, flame retardants, or various fillers such as vermiculite, inorganic fibers, quartz sand, glass microspheres, mica, silica, mineral wool, and the like.
  • auxiliaries such as solvents, such as xylene or toluene, wetting agents, for example based on polyacrylates and / or polyphosphates, antifoams, such as silicone defoamers, thickeners, such as alginate thickeners, dyes, fungicides, plasticizers, such as chlorine-containing waxes , Binders, flame retardants, or various fillers
  • rheology additives such as anti-settling agents, anti-sagging agents and thixotropic agents
  • rheology additives such as anti-settling agents, anti-sagging agents and thixotropic agents
  • rheology additives based on pyrogenic or precipitated silicas or based on silanized pyrogenic or precipitated silicas can be used.
  • the rheology additive is preferably fumed silicas, modified and unmodified phyllosilicates, precipitated silicas, cellulose ethers, polysaccharides, PU and acrylate thickeners, urea derivatives, castor oil derivatives, polyamides and fatty acid amides and polyolefins, if they are in solid form, pulverized celluloses and / or Suspending agents such as xanthan gum.
  • composition of the invention can be formulated as a two- or multi-component system.
  • the composition according to the invention is packaged as a two-component system, wherein the component A and the component B are arranged reaction-inhibiting separately. Accordingly, a first component, the component I, the component A and a second component, the component II, the component B contains. This ensures that the two components A and B of the binder are mixed together just prior to use and the curing reaction trigger. This makes the system easier to handle.
  • the unsaturated compound is preferably present in an amount of 2 to 95 wt .-%, contained in the component I.
  • component I If a reactive diluent is used, it is contained in component I in an amount of 90 to 10% by weight, preferably 70 to 10% by weight.
  • the thiol-functionalized compound is preferably in an amount of 0.5 to 90% by weight, more preferably in an amount of 2 to 85% by weight, and most preferably in my amount of 4 to 75% by weight in FIG of component II.
  • an inhibitor When an inhibitor is used, it may be contained in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, and more preferably 0.03 to 0.35% by weight, based on the compound with reactive carbon multiple bonds having one or more reactive C-C double bonds or C-C triple bonds per molecule (constituent A), contained in component I.
  • the free radical initiator is a mixture of a peroxide, an accelerator and optionally a co-accelerator or catalyst
  • the accelerator and the co-accelerator or the catalyst are expediently arranged in a reaction-inhibiting manner separate from the peroxide.
  • the two-component system preferably comprises the component A and the component B reaction inhibiting separately in different containers, such as a multi-chamber device, such as a multi-chamber cartridge from which containers the two components are pressed and mixed by the action of mechanical forces or under the action of a gas pressure.
  • the constituent C may be contained as a total mixture or divided into individual components in a first component I and / or in a second component II. The division of the component C is dependent on the compatibility of the compounds contained in the composition, so that neither a reaction of the compounds contained themselves or a mutual interference nor a reaction of these compounds can be carried out with the compounds of the other constituents. This depends on the connections used.
  • the intumescent additive is divided into component I and component II in such a way that component I contains at least part of the carbon source and at least one propellant and component II optionally contains part of the carbon source and at least one acid generator.
  • component I contains at least part of the carbon source and at least one propellant
  • component II optionally contains part of the carbon source and at least one acid generator.
  • at least one ash crust stabilizer is included in the composition, it may be contained in either component I or component II, or it may be divided into the two components I and II in a suitable manner. This ensures that the highest possible proportion of fillers can be achieved. This leads to high intumescence, even with low layer thicknesses of the composition.
  • the acid generator is included for storage stability reasons in the component II. As already mentioned above, compounds with CC double bonds or triple bonds are added to increase the storage stability of stabilizers.
  • the dehydrogenation catalyst that is to say the acid generator, which can contain acid traces as a result of the preparation, is therefore preferably stored separately from the component I.
  • the composition is applied as a paste with a brush, a roller or by spraying onto the substrate, in particular metallic substrate.
  • the composition is applied by means of an airless spray process.
  • the two- or multi-component composition according to the invention is characterized by a very rapid curing by free-radical polymerization and thus unnecessary drying. This is particularly important when the coated components have to be loaded or further processed quickly, either by coating with a cover layer or by moving or transporting the components. Also, the coating is thus much less susceptible to external influences on the construction site, such as e.g. Exposure to (rain) water or dust and dirt, which in water-based or solvent-based systems can lead to a washing out of water-soluble constituents such as ammonium polyphosphate, or in the absorption of dust to a reduced intumescence. Due to the low viscosity of the composition despite the high solids content, the composition remains easy to process, especially by common spray methods. Due to the low softening point of the binder and the high solids content, the expansion rate is high even at low layer thickness.
  • the two- or multi-component composition according to the invention is suitable as a coating, in particular as a fire protection coating, preferably sprayable coating for substrates on a metallic and non-metallic basis.
  • the substrates are not limited and comprise components, in particular steel components and Wooden components, but also individual cables, cable bundles, cable trays and cable ducts or other lines.
  • the composition according to the invention is mainly used in the construction sector as a coating, in particular fire protection coating for steel construction elements, but also for construction elements made of other materials, such as concrete or wood, as well as fire protection coating for individual cables, cable bundles, cable trays and cable ducts or other lines.
  • Another object of the invention is therefore the use of the composition according to the invention as a coating, in particular as a coating for construction elements or components of steel, concrete, wood and other materials, such as plastics, in particular as fire protection coating.
  • the present invention also relates to objects obtained when the composition of the invention has cured. The objects have excellent intumescent properties.
  • constituent B together with the ammonium polyphosphate and constituent A are mixed together with the remaining compounds of constituent C with the aid of a dissolver and homogenized.
  • component II and I are obtained.
  • these two mixtures are then mixed and applied either before spraying or preferably during spraying.
  • the curing behavior was observed, then the intumescent factor and the relative ash crustal stability were determined.
  • the Put masses each in a round Teflon mold about 2 mm deep and 48 mm in diameter.
  • the time for the curing corresponds to the time after which the samples were cured and the Teflon mold could be removed.
  • the mixture After mixing the three ingredients, the mixture cured to a white polymeric solid after 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition qui forme une couche isolante et qui contient un liant à base de thiol-ène. Grâce à la composition selon l'invention, dont le taux d'expansion est relativement élevé, des revêtements peuvent être appliqués avec l'épaisseur de couche nécessaire pour la durée de résistance au feu de manière simple et rapide, l'épaisseur de couche pouvant être réduite à un minimum et un grand effet isolant pouvant néanmoins être obtenu. La composition selon l'invention convient en particulier pour la protection anti-incendie, en particulier comme revêtement de substrats métalliques et/ou non métalliques, par exemple des éléments en acier tels que des étais, des poutres, ou des barres de treillis, pour accroître la durée de résistance au feu.
EP13811834.4A 2012-12-18 2013-12-10 Composition formant une couche isolante et son utilisation Pending EP2935470A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012223513.2A DE102012223513A1 (de) 2012-12-18 2012-12-18 Dämmschichtbildende Zusammensetzung und deren Verwendung
PCT/EP2013/076094 WO2014095491A1 (fr) 2012-12-18 2013-12-10 Composition formant une couche isolante et son utilisation

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EP2935470A1 true EP2935470A1 (fr) 2015-10-28

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US (1) US10287504B2 (fr)
EP (1) EP2935470A1 (fr)
DE (1) DE102012223513A1 (fr)
RU (1) RU2015129333A (fr)
WO (1) WO2014095491A1 (fr)

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EP3699242A1 (fr) 2019-02-21 2020-08-26 Hilti Aktiengesellschaft Composition intumescente aux caractéristiques mécaniques améliorées et son utilisation
EP3699241A1 (fr) 2019-02-21 2020-08-26 Hilti Aktiengesellschaft Composition intumescente à base d'époxyde aux caractéristiques mécaniques améliorées et son utilisation

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EP3699241A1 (fr) 2019-02-21 2020-08-26 Hilti Aktiengesellschaft Composition intumescente à base d'époxyde aux caractéristiques mécaniques améliorées et son utilisation

Also Published As

Publication number Publication date
DE102012223513A1 (de) 2014-06-18
WO2014095491A1 (fr) 2014-06-26
RU2015129333A (ru) 2017-01-23
US10287504B2 (en) 2019-05-14
US20150299578A1 (en) 2015-10-22

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